CN108841042A - Inorganic nano material and high polymerization degree APP compound flame redundant and preparation method thereof - Google Patents
Inorganic nano material and high polymerization degree APP compound flame redundant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses inorganic nano materials and high polymerization degree APP compound flame redundant and preparation method thereof；The preparation method first prepares component A high polymerization degree APP nano dispersion fluid：Deionized water and aqueous dispersion are subjected to mixed at high speed, high polymerization degree APP is added and continues mixed at high speed, strong broken dispersion obtains nano suspending liquid；Then B component inorganic fire retardants nano dispersion fluid is prepared：Deionized water, aqueous coupling agent and aqueous dispersion carry out mixed at high speed, add inorganic fire retardants and continues to mix, and strong broken dispersion obtains nano suspending liquid；By component A, B component and isolation dispersing agent emulsification, suspended nano dispersion emulsion is made；It is dry, obtain product.Nano material favorable dispersibility of the present invention, simple process, preparation cost are low, and inorganic nano material and high polymerization degree APP compound flame redundant and the compatibility of high molecular material substrate are good, and it is few to add usage amount.
Description
Technical field
The present invention relates to a kind of Halogen compound flame redundants, more particularly, to inorganic nano material and high polymerization degree polyphosphoric acid
The compound flame redundant and preparation method thereof that ammonium is compounded, the fire retardant are mainly used for the fire-retardant of high molecular material.
Background technique
Most of high molecular materials be all it is inflammable, addition fire retardant to high molecular material carry out flame retardant treatment, can hinder
Only high molecular material burns or delays the sprawling of the intensity of a fire.The fire retardant that China uses at present is mainly with organic halogenated flame retardant
It is main, although it and high-molecular organic material compatibility are good, good flame retardation effect, to add dosage seldom, to the mechanical performance shadow of material
The features such as smaller is rung, but organic halogenated flame retardant is larger there is smoke amount in combustion and releases toxic, rotten
The shortcomings that corrosion hydrogen halide.
Different from organic fire-retardant, halogen-free inorganic flame retardant has many advantages, such as Halogen, low cigarette, low toxicity, non-corrosive gas,
But there is using, additive amount is big and polymer base material affinity is poor, to height for now widely used halogen-free inorganic flame retardant
The disadvantages of processing technology and mechanical performance of molecular material are affected.Therefore, new and effective halogen-free inorganic high score is developed
Sub- fire proofing has become development priority.
103304846 A of Chinese invention patent application CN discloses a kind of ammonium polyphosphate and aluminum hydroxide nano-composite
And preparation method thereof；Its method be at a temperature of T1, by phosphorus pentoxide, diammonium hydrogen phosphate and urea or phosphorus pentoxide with
Diammonium hydrogen phosphate or phosphorus pentoxide and ammonium dihydrogen phosphate or diammonium hydrogen phosphate and urea or ammonium dihydrogen phosphate and urea, or
Reaction kettle is added in phosphoric acid and urea, heats after carrying out to reaction kettle；Aluminium hydroxide, the temperature of T1 are added when at T1 to 350 DEG C
Degree is room temperature to 250 DEG C；When being warming up to 150-300 DEG C, start to be passed through ammonia into system, ammonia pressure maintains normal pressure to 0.5
Megapascal keeps temperature-resistant, continues to be passed through ammonia 30-200min when reaction temperature is warming up to 250-350 DEG C；Finally cool down
To 200 DEG C hereinafter, obtaining the nano-complex of ammonium polyphosphate and aluminium hydroxide；During the reaction, system is stirred, powder
Broken or grinding.But the aluminium hydroxide that the technology is added is not nanoscale powder, only finally to obtained ammonium polyphosphate and hydrogen
The compound of aluminium oxide is stirred, crushes or grinds, and what is obtained is not nanoscale material.
Chinese invention patent application CN101348721 discloses a kind of ammonium polyphosphate and montmorillonite nano complex and its system
Preparation Method：The nano-complex preparation method is that montmorillonite is added at the initial stage of routinely preparation ammonium polyphosphate process, is warming up to 150
At DEG C -300 DEG C, it is passed through ammonia, heat preservation when being warming up to 300-350 DEG C continues ammonification 30-200 minutes, obtains ammonium polyphosphate and its
With the nano-complex of montmorillonite.But montmorillonite is added at the reaction process initial stage of routinely preparation ammonium polyphosphate in the technology, and
Nano-dispersed processing is not carried out to montmorillonite, does not solve the agglomeration traits of powder, which is not achieved nanocomposite.
106832414 A of Chinese invention patent application CN discloses a kind of nano-silicon dioxide modified ammonium polyphosphate
Preparation method：Include the following steps：1) the reactant phosphorus pentoxide and diammonium hydrogen phosphate of equimolar ratio are put into kneader,
Heat up logical ammonia after mixing evenly, and nano silica is added after reacting 0.5--5h at 180-320 DEG C, continues logical ammonia in 180-
0.5--5h is reacted at 320 DEG C, obtains nano-silicon dioxide modified ammonium polyphosphate crude product；It 2) will be nano-silicon dioxide modified
Kneader is added by crude product in polyphosphoric acids, sprays alkylsiloxane under agitation, reacts 0.5-3h at 80-180 DEG C,
Up to nano-silicon dioxide modified ammonium polyphosphate, nano-silicon dioxide modified ammonium polyphosphate is white powder.The technology exists
Silicon-dioxide powdery is added in the reaction process for preparing ammonium polyphosphate, does not carry out nanosizing dispersion to the powder that silica is reunited
Processing, sees from the table 1 of embodiment in invention, the partial size of obtained silica modified ammonium polyphosphate be 17 μm (i.e.
17000nm), which cannot get nanocomposite.
The inorganic fire retardants particle that the above-mentioned prior art uses generally in the micron-scale more than, flame resistant filler amount is big, fire-retardant
It is inefficient, all than more serious the problem of caused processing technology and properties of product.In addition its processing method or preparation method
The effect really dispersed can not be formed in fire retardant to inorganic nano material.It is well known that the agglomeration of nano material is
A most thorny issue in inorganic nano dispersion situation, will make nano material partial size reach 100nm or less and not roll into a ball
Poly- phenomenon, the above-mentioned prior art do not carry out the measure of nano-dispersed to inorganic nano material, and inorganic nano material is if it is solid
State powder state, can be due to attracting each other to causing agglomeration serious between material molecule.With regard to point of current nano material
For the technology of dissipating, even if being surface-treated to solid powder, it is also difficult to realize that agglomeration does not occur for solid nano material, most
Whole nano material can lose nano-meter characteristic because of reunion.
Liu Guosheng, Wu Na, Hao Jianwei etc. are ground in paper ammonium polyphosphate modifying/sepiolite collaboration expanded flame-retardant polypropylene application
Study carefully；(fire proofing and technology, the 6th phase in 2008) introduce addition nano material after make high molecule nano material mechanical property and
Flame retardant property significantly improves, the notable features such as high-modulus, stronger barrier action, high thermal stability, preferable mechanical property.
But what this article was introduced is by using ball mill by fire retardant, sepiolite, other auxiliary agents mixed grinding in proportion, obtained powder
Material is a kind of common common ore powder grinding technique from this technology for carrying out abrasive flour by ball mill, to powder
Polished is the nm regime that powder is not achieved, and especially powder can reunite rapidly again after powder grinding, loses a nanometer material
Expect performance.
Summary of the invention
The purpose of the invention is to overcome agglomeration of the inorganic nano material in halogen-free inorganic flame retardant, one is provided
The low inorganic nano material of kind nano material favorable dispersibility, simple process, preparation cost is compounded with high polymerization degree APP
Fire retardant compound and preparation method thereof, the present invention prepared by inorganic nano material and high polymerization degree APP Compositional type hinder
It fires agent and the compatibility of high molecular material substrate is good, and it is few to add usage amount.
Major measure of the present invention is：1) by the way that nano material is prepared as aqueous solution, in particular by dispersing agent and
Interleaving agent carries out cladding isolation to nano particle, effectively overcomes the agglomeration traits of nano particle；2) of the invention by aqueous solution
It is dried, evaporates deionized water, and the effective components such as interleaving agent are still coated on nano-grain, this makes to make
Standby nano-meter flame retardants out can keep nano-scale and corresponding nano ZnO for a long time.3) present invention utilizes the side of aqueous solution
Nanometer high polymerization degree APP compound in nano-level with inorganic nano fire retardant by formula, improves inorganic fire retardants and height
Compatibility between molecular material matrix, and achieve the purpose that reduce amount of flame-retardant agent and improve flame retardant property.
Traditional inorganic fire retardants generally can be divided into three kinds of mechanism, i.e. separation layer mechanism, heat absorption mechanism and diluents mechanism.This hair
Bright proposed inorganic nano fire retardant, which is inorganic nano-particle not only with high polymerization degree APP cooperative flame retardant mechanism, to be had
Every fire retardant mechanism of the above conventional flame retardant, simultaneously because the unique size of nanoparticle and surface-active.
Technical solution of the present invention implementation is as follows：
The preparation method of inorganic nano material and high polymerization degree APP compound flame redundant, including steps are as follows：
1) preparation of component A high polymerization degree APP nano dispersion fluid：Deionized water and aqueous dispersion are carried out high
Speed mixing adds high polymerization degree APP and continues mixed at high speed 2-4 hours, then collides dispersing apparatus pair by high-pressure jet
Mixture carries out strong broken dispersion 2-4 hours, and jet stream impact pressure is 100-200PMa, by the high polymerization degree polyphosphoric acid of reunion
Ammonium powder carries out depolymerization and is separated into nano suspending liquid；In terms of mass fraction, which is：20-30 parts high polymerization
Spend ammonium polyphosphate, 60-70 parts of deionized waters, 5-15 parts of aqueous dispersions；
2) preparation of B component inorganic fire retardants nano dispersion fluid：Deionized water, aqueous coupling agent and aqueous dispersion carry out
Mixed at high speed adds inorganic fire retardants and continuess to mix 2-4 hours, then collides broken point strongly of dispersing apparatus by high-pressure jet
It dissipates 2-4 hours, jet stream impact pressure is 100-200PMa, and the powders of reunion are carried out depolymerization and are separated into nanometer
Suspension；In terms of mass fraction, which is：20-30 parts of inorganic fire retardantss, 60-70 parts of deionized waters, 5-15 parts
Aqueous dispersion and 1-5 parts of aqueous coupling agents；
3) by component A, B component and isolation dispersing agent in mass ratio 1：0.5‐1.5：0.5-1.5 carries out cream on mulser
Change, suspended nano dispersion emulsion is made, control 90% percent of pass of partial size is 80-110nm；
4) prepared suspended nano dispersion emulsion is dry, it obtains inorganic nano and high polymerization degree APP Compositional type hinders
Fire agent；
The isolation dispersing agent is polyvinyl alcohol, EVA (ethane-acetic acid ethyenyl (vinyl acetate) ester copolymer), plasticising
Agent or aqueous silicone oil；
Aqueous coupling agent described in step 2) is all soluble silane coupling agent, water-soluble titanate coupling agent or water solubility
Aluminate coupling agent；
Aqueous dispersion described in step 1) and step 2) is dispersing agent DISPER BYK-180, dispersant B YK-154, divides
Powder DISPER BYK-193, easily happy DS-171 is applied, easily happy DS-191 is applied, applies easily happy DS-194, dispersing agent SN-5040, dispersion
Agent TEGO740W, dispersing agent EFKA-4530 or dispersing agent EFKA6230.
To further realize the object of the invention, it is preferable that the high polymerization degree APP is polymerization degree n >'s 1000
Branched II ammonium polyphosphate of APP crystalline phase (APP II).
Preferably, the inorganic fire retardants is aluminium hydroxide fire retardant (ATH), flame retardant of magnesium hydroxide (MDH), red phosphorus
One of fire retardant, zinc borate, antimony oxide, molybdenum compound, phyllosilicate and anhydrous magnesium carbonate are a variety of.
Preferably, the revolving speed of step 1) and the step 2) mixed at high speed is 1000-3000 revs/min.
Preferably, the drying temperature is 40-120 DEG C, and the dry time is 5-20h.
Preferably, the high-pressure jet collides dispersing apparatus model MN-200K, and highest processing pressure is 200MPa.
Preferably, the plasticizer be dioctyl phthalate, diisooctyl phthalate, epoxidized soybean oil,
Tributyl 2-acetylcitrate (ATBC).
Preferably, the aqueous silicone oil is aqueous silicone oil TS-8311, polyether modified siloxane SI-204 or amido silicon oil
C910。
A kind of inorganic nano material and high polymerization degree APP compound flame redundant, are made by above-mentioned preparation method,
After the inorganic nano material is compounded with high polymerization degree APP, 90% percent of pass of partial size (D90) that compound flame redundant includes
It is not soluble in water in 80-110nm；Environmental-friendly with highly effective flame-retardant, additive amount is few, and mechanical performance influences the good characteristics such as small.
Life smoke when feature most outstanding is burning is extremely low, does not generate hydrogen chloride.
Compared with the existing technology, the present invention has following features：
1) feature of the present invention is the method using aqueous dispersion, using high-pressure jet collision dispersing apparatus respectively to poly- phosphorus
Sour ammonium and inorganic fire retardants carry out nanosizing processing, obtain composite Nano dispersion fire retardant.
2) present invention enhances resistance using quantum size effect possessed by inorganic nano-particle, high-specific surface area effect etc.
The interface interaction between agent and high molecular material is fired, the compatibility between inorganic fire retardants and high molecular material matrix is improved, and
Achieve the purpose that reduce amount of flame-retardant agent and improves flame retardant property.The high energy of nano-powder, ultra-fine and high activity answer its powder
Have a great impact with performance.It is inorganic with the reduction of inorganic nano fire-retardant particles partial size and the reduction of fire retardant additive amount
Influence of the fire retardant to high molecular material performance is obviously reduced；And inorganic nanoparticles as retardant fillers through full and uniform
After dispersion, reduce the dosage of fire retardant, and shock resistance to high molecular material and flame retardant property are also
Improve.The evenly dispersed interaction enhanced between inorganic fire retardants and high molecular material basal body interface of nano material, makes
Inorganic fire retardants can be more evenly dispersed in high molecular material matrix, play with rigid nanoparticle to high molecular material into
The effect of row plasticising enhancing, so the mechanical performance of final macromolecule material product can be improved largely.
3) present invention is compounded using nanometer high polymerization degree APP with inorganic nano fire retardant, prepares a kind of nanometer
Fire retardant compound, has the characteristics that good dispersion, measures through nanoparticle through analyzer, and particle dispersion particle diameter distribution major part exists
100nm or less.
4) fire retardant of the present invention has many advantages, such as Halogen, nontoxic, low cigarette, and flame retarding efficiency is high, the few spy of fire retardant additive amount
Point；The additive amount 5-10% of fire retardant of the present invention, and the fire retardant additive amount of conventional method is 20-40%；And invention is fire-retardant
For rank up to UL-94V-0 grades, limit oxygen index is and good with high molecular material substrate affinity up to 38% or more；
4) fire retardant preparation process of the present invention is simple, convenient and reliable operation, safety and environmental protection, and manufacturing cost is low.
Detailed description of the invention
Fig. 1 is the test distribution map of suspension nano-dispersed emulsion particle diameter prepared by embodiment 1.
Fig. 2 is the test distribution map of suspension nano-dispersed emulsion particle diameter prepared by embodiment 2.
Fig. 3 is the test distribution map of suspension nano-dispersed emulsion particle diameter prepared by embodiment 3.
Specific embodiment
For a better understanding of the invention, the present invention will be further explained with reference to the examples below, but reality of the invention
It is unlimited so to apply mode.
II type ammonium polyphosphate APP 101 of high polymerization degree of the present invention, the degree of polymerization are greater than 1000, divide greatly for inorganic straight chain
Sub- polymer, product P, N content are high, and thermostabilization and chemical stability are good, and for product close to neutrality, water-soluble and hygroscopicity is small,
It is nontoxic, it is good with substrate, auxiliary agent conformability in application process, it is non-volatile, do not generate corrosive gas, securely and reliably.Its performance
Index is as follows：
Embodiment 1
A kind of preparation method of inorganic nano material and high polymerization degree APP compound flame redundant, including step is such as
Under：
(1) high polymerization degree APP nano dispersion fluid abbreviation component A, in terms of mass fraction, composition of raw materials group becomes：
101 20 parts of II type ammonium polyphosphate APP of high polymerization degree
70 parts of deionized water
5 parts of aqueous dispersion DISPER BYK-180
When preparation, deionized water and aqueous dispersion are carried out mixed at high speed first, add high polymerization degree APP
It continuess to mix 2 hours, revolving speed when mixed at high speed is 1500 revs/min；Dispersing apparatus (model is collided by high-pressure jet again
MN-200K dispersion 3 hours) is carried out to the mixture, jet stream impact pressure takes 100PMa, and the mixture is made to be separated into nanoparticle suspension
Liquid.
(2) inorganic fire retardants nano dispersion fluid abbreviation B component, in terms of mass fraction, composition of raw materials group becomes：
When preparation, deionized water and aqueous dispersion and aqueous coupling agent are carried out mixed at high speed first, added inorganic
Fire retardant continuess to mix 2 hours, and mixed at high speed revolving speed is 1500 revs/min；Dispersing apparatus (model is collided by high-pressure jet again
MN-200K broken dispersion 3 hours) is carried out to the mixture, jet stream impact pressure takes 150PMa, and the mixture is made to be separated into nanometer
Suspension.
(3) by component A obtained, B component and polyvinyl alcohol (isolation dispersing agent) in mass ratio 1：1：1 mixing, is put into cream
Emulsification treatment is carried out in change machine, suspension nano-dispersed lotion is made, and 90% percent of pass of partial size (D90) reaches 105nm, such as schemes
Shown in 1.Partial size test is to measure (HORIBALaser Scattering Particle Size using laser particle instrument
Distribution Analyzer), find out from the grain size distribution of Fig. 1, particle diameter distribution largely falls in 100nm hereinafter, D90
For 0.105 μm (i.e. 105nm).
(4) suspended nano dispersion emulsion obtained is placed in drying machine, dry 5h, is made inorganic under the conditions of 100 DEG C
Nano material (aluminium hydroxide) and high polymerization degree APP compound flame redundant.
Embodiment 2
A kind of preparation method of inorganic nano material and high polymerization degree APP compound flame redundant, including step is such as
Under：
(1) in terms of mass fraction, high polymerization degree APP nano dispersion fluid (A group is prepared according to the following raw material formula
Point)：
101 25 parts of II type ammonium polyphosphate APP of high polymerization degree
65 parts of deionized water
Aqueous dispersion applies easily 5 parts of happy DS-171
When preparation, deionized water and aqueous dispersion are carried out mixed at high speed first, add high polymerization degree APP
It continuess to mix 2 hours, revolving speed when mixed at high speed is 1500 revs/min；Dispersing apparatus (model is collided by high-pressure jet again
MN-200K dispersion 3.5 hours) is carried out to the mixture, jet stream impact pressure takes 160PMa, so that the mixture is separated into nanometer outstanding
Supernatant liquid.
(2) in terms of mass fraction, inorganic fire retardants nano dispersion fluid (B component) is prepared according to the following raw material formula：
When preparation, deionized water and aqueous dispersion and aqueous coupling agent are carried out mixed at high speed first, added inorganic
Fire retardant continuess to mix 2 hours, and mixed at high speed revolving speed is 1500 revs/min；Dispersing apparatus (model is collided by high-pressure jet again
MN-200K broken dispersion 4 hours) is carried out to the mixture, jet stream impact pressure takes 150PMa, and the mixture is made to be separated into nanometer
Suspension.
(3) by Part A components obtained, B component and EVA (isolation dispersing agent) in mass ratio 1：1：1 mixing, is put into emulsification
Emulsification treatment is carried out in machine, suspension nano-dispersed lotion is made, and 90% percent of pass of partial size (D90) reaches 98nm.Such as Fig. 2 institute
Show.Partial size test is to measure (HORIBA Laser Scattering Particle Size using laser particle instrument
Distribution Analyzer), find out from the grain size distribution of Fig. 2, particle diameter distribution largely falls in 100nm hereinafter, D90
For 0.98 μm (i.e. 98nm).
(4) suspended nano dispersion emulsion obtained is placed in drying machine, dry 5h, is made inorganic under the conditions of 100 DEG C
Nano material (magnesium hydroxide) and high polymerization degree APP compound flame redundant.
Embodiment 3
A kind of preparation method of inorganic nano material and high polymerization degree APP compound flame redundant, including step is such as
Under：
(1) in terms of mass fraction, high polymerization degree APP nano dispersion fluid (A group is prepared according to the following raw material formula
Point)：
101 30 parts of II type ammonium polyphosphate APP of high polymerization degree
55 parts of deionized water
7 parts of aqueous dispersion (dispersing agent EFKA-4530)
When preparation, deionized water and aqueous dispersion are carried out mixed at high speed first, add high polymerization degree APP
It continuess to mix 2 hours, revolving speed when mixed at high speed is 1500 revs/min；Dispersing apparatus, model are collided by high-pressure jet again
MN-200K carries out dispersion 2 hours to the mixture, and jet stream impact pressure takes 150PMa, and the mixture is made to be separated into nanoparticle suspension
Liquid.
(2) in terms of mass fraction, inorganic fire retardants nano dispersion fluid (B component) is prepared according to the following raw material formula：
When preparation, deionized water and aqueous dispersion and aqueous coupling agent are carried out mixed at high speed first, added inorganic
Fire retardant continuess to mix 3 hours, and mixed at high speed revolving speed is 1500 revs/min；Dispersing apparatus, model are collided by high-pressure jet again
MN-200K carries out broken dispersion 3 hours to the mixture, and jet stream impact pressure takes 180PMa, and the mixture is made to be separated into nanometer
Suspension.
(3) by component A obtained, B component and tributyl 2-acetylcitrate (isolation dispersing agent) in mass ratio 1：1：1 is mixed
It closes, is put into mulser and carries out emulsification treatment, suspension nano-dispersed lotion is made, 90% percent of pass of partial size (D90) reaches
108nm.As shown in Figure 3.Partial size test is to measure (HORIBALaser Scattering Particle using laser particle instrument
Size Distribution Analyzer), find out from the grain size distribution of Fig. 3, particle diameter distribution largely fall in 100nm with
Under, D90 is 0.108 μm (i.e. 108nm).
(4) suspended nano dispersion emulsion obtained is placed in drying machine, dry 5h, is made inorganic under the conditions of 100 DEG C
Nano material (zinc borate) and high polymerization degree APP compound flame redundant.
Comparative example
Comparative example is the embodiment 1 of Chinese invention patent application CN 106832414A；A kind of nanometer two disclosed in this application
Silica modified ammonium polyphosphate composition of raw materials is as follows:
In Chinese invention patent application CN 106832414A embodiment 1：The system of nano-silicon dioxide modified ammonium polyphosphate
Preparation Method is：
1) the reactant phosphorus pentoxide and diammonium hydrogen phosphate that equimolar ratio is put into kneader, heat up after mixing evenly
Logical ammonia, in terms of every 100 kilograms of reactants, leading to ammonia amount is 1m3/ h is incorporated as phosphorus pentoxide and phosphorus after reacting 5h at 180 DEG C
Sour hydrogen diammonium gross mass 0.02%, the nano silica that partial size is 5nm continue logical ammonia and react 5h at 180 DEG C, with every 100
Kilogram reactant meter, leading to ammonia amount is 0.1m3/ h, obtaining white solid powder is that nano-silicon dioxide modified ammonium polyphosphate is thick
Product；
2) kneader is added in nano-silicon dioxide modified ammonium polyphosphate crude product, is 60 revs/min in revolving speed and stirs
Sprinkling is the gamma-aminopropyl-triethoxy silicon of nano-silicon dioxide modified ammonium polyphosphate crude product quality 0.5% under the conditions of mixing
Alkane reacts 0.5h at 80 DEG C to get nano-silicon dioxide modified ammonium polyphosphate.There it can be seen that preparation method does not have
It describes and the nanosizing of silica is handled, the preparation method in patent of invention is to cannot get nano-silicon dioxide modified poly
Ammonium phosphate.
The fire retardant of 1-3 of embodiment of the present invention preparation and the flame retardant performance comparison of comparative example preparation are as shown in table 1, are adopted
Substrate is polypropylene；Substrate example 5% in mass ratio, 8%, 10% is added the inorganic nano of 1-3 of embodiment of the present invention preparation
Material and high polymerization degree APP compound flame redundant, test its flame retardant property.Combustion rating, limit oxygen index, drawing in table 1
Stretch intensity, the test method of impact strength and foundation：
Oxygen index (OI):GB 2406.2‐2008；
Vertical combustion:GB 2408‐2008；
Tensile strength:GB 1040‐2006；
Simply supported beam notch impact strength：GB 1843‐2008.
By table 1 it will be evident that the partial size of the composite flame-retardant agent of comparative example is at 17 μm, 20% composite flame-retardant agent ability is added
Flame retardant effect, oxygen index (OI) 32% can be reached.In the embodiment of the present invention, inorganic nano fire retardant and the poly- phosphorus of high polymerization degree are utilized
Sour ammonium cooperative flame retardant effect, the characteristics of taking into account both inorganic nano fire retardant and high polymerization degree APP, prepare Compositional type resistance
The partial size of agent is fired in 100nm or so, and average grain diameter is greatly reduced, and additive amount of the fire retardant in macromolecule matrix material obviously subtracts
Few, the combustion rating of high molecular material flame retardant property reaches UL-94V-0,38% or more limit oxygen index.Mechanical strength (stretches
Intensity and impact strength) it is improved.
1 embodiment of table is compared with the performance of comparative example
Poor compatibility between prior art halogen-free inorganic flame retardant and high molecular material matrix, and to high molecular material machine
The negative effect of tool performance is larger, and engineering is caused to be difficult to be widely applied in practice.And now widely used inorganic fire retardants,
Its grain diameter generally in the micron-scale more than, loading of the inorganic fire retardants in high molecular material is big, flame retarding efficiency is not high, and
As the high molecular material caused by it processing technology and properties of product the problems such as all than more serious.Inorganic nano of the present invention is fire-retardant
Agent is that 100nm micro-denier flame resistant particle below forms by grain diameter, it is only necessary to be added in high molecular material matrix few
This inorganic nano fire retardant of amount, can significantly reduce the flame retardant property of high molecular material, and this inorganic nano is fire-retardant
The addition of agent can also be such that the mechanical performance of high molecular material improves.Therefore inorganic nano technology is fire-retardant in traditional high molecular material
Application in agent is that flame-retarded technology opens a new field.
The present invention is compound by inorganic nano fire retardant and high polymerization degree APP, poly- using inorganic nano fire retardant and height
Right ammonium polyphosphate synergetic flame-retardant effect, the characteristics of taking into account both inorganic nano fire retardant and high polymerization degree APP, can
Improve the flame retardant property of high molecular material, and its mechanical performance can be made significantly to be improved.It is embodied in following several respects：
The present invention is enhanced using quantum size effect, high-specific surface area effect possessed by inorganic nano-particle itself etc.
Interface interaction improves the compatibility of inorganic matter and high molecular material matrix, can reach and reduces amount of flame-retardant agent and improve anti-flammability
The purpose of energy.Above-described embodiment and comparative example prove the high energy of inorganic nanometer powder and high activity be applied to performance have it is very big
It influences.
With the reduction of inorganic nano material partial size and the reduction of fire retardant additive amount, the present invention contains inorganic nano material
Halogen-free flame retardants positive influences are become from negative effect to high molecular material performance；Because the nano-dispersedization of inorganic material increases
The strong interaction of fire retardant and high molecular material basal body interface, allow fire retardant more evenly be dispersed in high molecular material
In matrix, as shown in table 1, the rigid particles of this inorganic nano material can play the work of plasticising enhancing to high molecular material matrix
With so that the mechanical performance and flame retardant property of high molecular material greatly improve.
Above embodiment just for the sake of clearly demonstrating examples made by the present invention is implemented to the present invention
The restriction of mode.For those of ordinary skill in the art, not similar shape can also be made on the basis of the above description
The variation or variation of formula.There is no necessity and possibility to exhaust all the enbodiments.It is all in the spirit and principles in the present invention
Within made any modifications, equivalent replacements, and improvements etc., be all contained within the scope of protection of the claims of the present invention.
Claims (9)
1. the preparation method of inorganic nano material and high polymerization degree APP compound flame redundant, it is characterised in that including step
It is as follows：
1) preparation of component A high polymerization degree APP nano dispersion fluid：It is mixed that deionized water and aqueous dispersion are subjected to high speed
It closes, adds high polymerization degree APP and continue mixed at high speed 2-4 hours, then dispersing apparatus is collided to mixing by high-pressure jet
Object carries out strong broken dispersion 2-4 hours, and jet stream impact pressure is 100-200PMa, by the high polymerization degree APP powder of reunion
End carries out depolymerization and is separated into nano suspending liquid；In terms of mass fraction, which is：20-30 parts of high polymerization degrees are poly-
Ammonium phosphate, 60-70 part deionized water, 5-15 parts of aqueous dispersions；
2) preparation of B component inorganic fire retardants nano dispersion fluid：Deionized water, aqueous coupling agent and aqueous dispersion carry out high speed
Mixing, adds inorganic fire retardants and continuess to mix 2-4 hours, then collides the strongly broken dispersion 2- of dispersing apparatus by high-pressure jet
4 hours, jet stream impact pressure was 100-200PMa, and the powders of reunion are carried out depolymerization and are separated into nanoparticle suspension
Liquid；In terms of mass fraction, which is：20-30 parts of inorganic fire retardantss, 60-70 parts of deionized waters, 5-15 parts it is aqueous
Dispersing agent and 1-5 parts of aqueous coupling agents；
3) by component A, B component and isolation dispersing agent in mass ratio 1：0.5‐1.5：0.5-1.5 is emulsified on mulser, system
Suspended nano dispersion emulsion is obtained, control 90% percent of pass of partial size is 80-110nm；
4) prepared suspended nano dispersion emulsion is dry, it obtains inorganic nano and high polymerization degree APP Compositional type is fire-retardant
Agent；
The isolation dispersing agent is polyvinyl alcohol, EVA, plasticizer or aqueous silicone oil；
Aqueous coupling agent described in step 2) is all soluble silane coupling agent, water-soluble titanate coupling agent or water-soluble aluminic acid
Ester coupling agent；
Aqueous dispersion described in step 1) and step 2) is dispersing agent DISPER BYK-180, dispersant B YK-154, dispersing agent
DISPER BYK-193, easily happy DS-171 is applied, easily happy DS-191 is applied, applies easily happy DS-194, dispersing agent SN-5040, dispersing agent
TEGO740W, dispersing agent EFKA-4530 or dispersing agent EFKA6230.
2. the preparation side of inorganic nano material according to claim 1 and high polymerization degree APP compound flame redundant
Method, which is characterized in that the high polymerization degree APP is the poly- phosphorus of branched APP crystalline phase II of polymerization degree n > 1000
Sour ammonium.
3. the preparation side of inorganic nano material according to claim 1 and high polymerization degree APP compound flame redundant
Method, which is characterized in that the inorganic fire retardants is aluminium hydroxide fire retardant, flame retardant of magnesium hydroxide, red phosphorus combustion inhibitor, boric acid
One of zinc, antimony oxide, molybdenum compound, phyllosilicate and anhydrous magnesium carbonate are a variety of.
4. the preparation side of inorganic nano material according to claim 1 and high polymerization degree APP compound flame redundant
Method, which is characterized in that the revolving speed of step 1) and the step 2) mixed at high speed is 1000-3000 revs/min.
5. the preparation side of inorganic nano material according to claim 1 and high polymerization degree APP compound flame redundant
Method, which is characterized in that the drying temperature is 40-120 DEG C, and the dry time is 5-20h.
6. the preparation side of inorganic nano material according to claim 1 and high polymerization degree APP compound flame redundant
Method, which is characterized in that the high-pressure jet collides dispersing apparatus model MN-200K, and highest processing pressure is 200MPa.
7. the preparation side of inorganic nano material according to claim 1 and high polymerization degree APP compound flame redundant
Method, which is characterized in that the plasticizer is dioctyl phthalate, diisooctyl phthalate, epoxidized soybean oil, second
Acyl tributyl citrate.
8. the preparation side of inorganic nano material according to claim 1 and high polymerization degree APP compound flame redundant
Method, which is characterized in that the aqueous silicone oil is aqueous silicone oil TS-8311, polyether modified siloxane SI-204 or amido silicon oil
C910。
9. a kind of inorganic nano material and high polymerization degree APP compound flame redundant, which is characterized in that it is by claim
The described in any item preparation methods of 1-8 are made, and partial size 80-110nm is not soluble in water.
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